JP6848059B2 - Propylene-based polymer, its production method, propylene-based resin composition and molded article - Google Patents

Description

The present invention relates to a propylene-based polymer having an unprecedented level of high stereoregularity, a method for producing the same, a propylene-based resin composition containing the propylene-based polymer, and the propylene-based polymer or the propylene-based resin composition. Concerning a molded body composed of.

Conventionally, a Ziegler-Natta catalyst composed of a titanium catalyst component and an organoaluminum compound has been widely used as a catalyst for producing polyolefin.

In particular, when producing a highly stereoregular polyolefin such as polypropylene, a solid titanium catalyst component containing an internal donor (internal electron donor), an organoaluminum compound, and an external donor (external electron donor) are usually used. A catalyst consisting of is used. For example, a magnesium chloride-supported solid titanium catalyst containing carboxylic acid esters as an internal donor, and an olefin polymerization catalyst composed of an organosilicon compound as an external donor together with an organoaluminum compound are known (for example, Patent Document 1). And 2).

However, when an olefin is polymerized using a catalyst containing a solid titanium catalyst component as described above, the so-called "surplus titanium compound" causes a problem that a polyolefin having high stereoregularity and a polyolefin having low stereoregularity are produced as a by-product. There was a point (Japanese Patent Laid-Open No. 59-124909).

On the other hand, in recent years, the automobile industry has been actively developing environmentally friendly fuel-efficient vehicles, and in the field of automobile materials as well, there is a demand for resinization and further thinning of materials for the purpose of weight reduction. For this reason, there are great expectations for improvement in propylene-based materials, which have many achievements as automobile materials such as bumper materials, and propylene-based weight with high rigidity and high heat resistance, which has an unprecedented level of high stereoregularity. Coalescence is required.

Japanese Unexamined Patent Publication No. 08-003215 Japanese Unexamined Patent Publication No. 08-143620 JP-A-59-124909

In view of the above-mentioned prior art, the present invention provides a propylene-based polymer having an unprecedented level of high stereoregularity, high rigidity and high heat resistance, and the high stereoregularity. A method for stably producing a sex propylene polymer with a small amount of by-product of low stereoregular polypropylene, high activity and stability, a resin composition containing the highly stereoregular propylene polymer, and the high stereoregulation. An object of the present invention is to provide a molded product formed by using a sex propylene-based polymer or the resin composition.

Further, in order to realize further thinning, a propylene-based polymer having unprecedented high stereoregularity, high rigidity and high heat resistance is particularly required in a high MFR region having excellent moldability (fluidity). It is also an object of the present invention to provide a highly stereoregular propylene-based polymer having a high MFR region or a molded product formed by using a resin composition containing the propylene-based polymer.

As a result of diligent studies to solve the above problems, the present inventors have made an extremely long meso-chain (α-) by polymerizing propylene in combination with, for example, a specific solid titanium catalyst component and a specific external donor. A propylene-based weight with unprecedented levels of high stereoregularity, which has a propylene unit chain in which methyl carbon is oriented in the same direction) and a TREF (heated elution fractionation measurement method) high-temperature elution component in relation to MFR. We found that coalescence was obtained. Further, for example, by polymerizing propylene in combination with a specific solid titanium catalyst component and a specific external donor, the highly stereoregular propylene-based polymer can be produced with a small amount of by-product of low stereoregular polypropylene. We have found that it can be obtained stably with high activity, and have completed the present invention.

The propylene-based polymer according to the present invention is characterized by satisfying the following requirements (1) to (4), and more preferably satisfies the following requirements (5).
(1) The meso average chain length is 8 to 100,000;
(2) The melt flow rate (MFR) (ASTM D1238, 230 ° C., under 2.16 kg load) is 0.5-1000 g / 10 min;
(3) The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is 4.2 to 20;
(4) When the ratio of the components eluted at a temperature of 122 ° C. or higher is A% by weight and the melt flow rate of the above requirement (2) is Bg / 10 minutes by the temperature rise elution fractionation measurement method (TREF), the following formula is used. Satisfy (I);
100 ≧ A ≧ 20 × EXP (−0.01 × B) ・ ・ ・ (I)
(5) The amount of the n-decane-soluble component at 23 ° C. is 0.01 to 2% by weight.

The propylene polymer of the present invention can be produced by polymerizing propylene in the presence of a catalyst for olefin polymerization, and the catalyst for olefin polymerization is, for example,
(I) A solid titanium catalyst component containing magnesium, titanium, halogen and an electron donor and satisfying the following requirements (k1) to (k4).
(Ii) The organosilicon compound component represented by the following formula (II) and
(Iii) A catalyst [A] containing an organometallic compound component containing an element belonging to Group 1, Group 2, or Group 13 of the Periodic Table, or
A catalyst [B] containing a prepolymerization catalyst (p) in which propylene is prepolymerized on the catalyst [A], the organosilicon compound component (ii), and the organometallic compound component (iii).
Is.

(K1) Titanium content is 2.5% by weight or less;
(K2) The content of the electron donor is 8 to 30% by weight;
(K3) Electron donor / titanium (weight ratio) is 7 or more;
(K4) Titanium is not substantially desorbed by hexane washing at room temperature.

R ¹ Si (OR ² ) ₂ (NR ³ R ⁴ ) ・ ・ ・ (II)
In formula (II), R ¹ represents a secondary or tertiary hydrocarbon group having 1 to 20 carbon atoms, R ² represents a hydrocarbon group having 1 to 4 carbon atoms, and R ³ represents a hydrocarbon group having 1 to 12 carbon atoms. Indicates a hydrocarbon group or a hydrogen atom of, and R ⁴ indicates a hydrocarbon group having 1 to 12 carbon atoms.

The solid titanium catalyst component (i) is
(A) Solid titanium, which contains magnesium, titanium, halogen and electron donors, and titanium is not desorbed by hexane washing at room temperature.
(B) Aromatic hydrocarbons,
It can be produced by a method including (c) contacting liquid titanium and (d) an electron donor.

The propylene-based resin composition of the present invention is characterized by containing the propylene-based polymer of the present invention.

The molded product of the present invention is characterized by being formed by using the propylene-based polymer or the propylene-based resin composition of the present invention.

According to the present invention, a highly rigid and highly heat-resistant propylene-based polymer having an unprecedented level of high stereoregularity can be obtained by having an extremely long meso-chain and a TREF high-temperature elution component. Be done. Further, according to the production method of the present invention, the propylene polymer can be produced stably with high activity, and the amount of by-product of low stereoregular polypropylene is small.

Hereinafter, the present invention will be described in detail.

[Propene polymer]
The first aspect of the propylene-based polymer of the present invention is characterized by satisfying the following requirements (1) to (4), and the second aspect of the propylene-based polymer of the present invention is the following requirements (1) to (1) to. It is characterized by satisfying (5). Hereinafter, the first aspect and the second aspect are collectively referred to as "the propylene-based polymer of the present invention".
(1) The meso average chain length is 8 to 100,000;
(2) The melt flow rate (MFR) (ASTM D1238, 230 ° C., under 2.16 kg load) is 0.5-1000 g / 10 min;
(3) The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is 4.2 to 20;
(4) When the ratio of the components eluted at a temperature of 122 ° C. or higher is A% by weight and the melt flow rate of the above requirement (2) is Bg / 10 minutes by the temperature rise elution fractionation measurement method (TREF), the following formula is used. Satisfy (I);
100 ≧ A ≧ 20 × EXP (−0.01 × B) ・ ・ ・ (I)
(5) The amount of n-decane-soluble component at 23 ° C. is 0.01 to 2% by weight;
Each requirement will be described below.

<Requirement (1)>
The propylene-based polymer of the present invention has a meso-average chain length of 8 to 100,000, preferably 900 to 50,000, and more preferably 1000 to 10000. When the meso-average chain length is within the above range, the stereoregularity of the propylene-based polymer is sufficiently high, and the mechanical properties such as heat resistance and flexural modulus of the propylene-based polymer are improved. The meso-average chain length can be determined by the method described in Examples described later.

<Requirement (2)>
The propylene-based polymer of the present invention has an MFR (ASTM D1238, 230 ° C., under a load of 2.16 kg) of 0.5 to 1000 g / 10 minutes, preferably 1.0 to 800 g / 10 minutes, more preferably 1.5 minutes. ~ 500 g / 10 minutes. When the MFR is within the above range, the balance between the moldability of the propylene-based polymer and the mechanical strength is excellent. The propylene-based polymer of the present invention has never been used in a high MFR region of preferably 50 to 1000 g / 10 minutes, more preferably 100 to 1000 g / 10 minutes, and particularly preferably 100 to 500 g / 10 minutes. Has a high level of stereoregularity.

<Requirement (3)>
The propylene-based polymer of the present invention has a ratio (Mw / Mn) of a weight average molecular weight (Mw) to a number average molecular weight (Mn) measured by GPC of 4.2 to 20, preferably 4.5 to 15. It is preferably 4.8 to 10. When Mw / Mn is within the above range, it is preferable from the viewpoint of moldability of the propylene-based polymer.

<Requirement (4)>
In the propylene-based polymer of the present invention, when the proportion of the component eluted at a temperature of 122 ° C. or higher by TREF is A% by weight and the melt flow rate of the above requirement (2) is Bg / 10 minutes, the following formula (I) ) Satisfies.

100 ≧ A ≧ 20 × EXP (−0.01 × B) ・ ・ ・ (I)
A propylene-based polymer satisfying the above formula (I) is preferable in that it has a stereoregularity showing a certain degree of heat resistance and high rigidity even if the MFR is a certain level or more.

<Requirement (5)>
In the second aspect of the propylene-based polymer of the present invention, the amount of the n-decane-soluble component at 23 ° C. is 0.01 to 2% by weight, preferably 0.1 to 1.8% by weight, more preferably 0. It is 2 to 1.5% by weight. When the amount of the decan-soluble component is within the above range, the highly crystalline component is sufficiently secured, and the by-product of the low stereoregular component is suppressed.

The above-mentioned propylene-based polymer of the present invention can be obtained by polymerizing propylene in the presence of a catalyst for olefin polymerization described later.

The propylene-based polymer of the present invention preferably satisfies the following requirement (6) in addition to the above requirements (1) to (4) or the above requirements (1) to (5), and further, the following requirement ( It is more preferable to satisfy 7) at the same time.
(6) The proportion of components eluted by TREF at a temperature of 122 ° C. or higher is 0.1 to 100% by weight;
(7) ^{13 The} mesopentad fraction (mm mm) determined by C-NMR is 99.4 to 100%.

<Requirement (6)>
In the propylene-based polymer of the present invention, the proportion A of the components eluted by TREF at a temperature of 122 ° C. or higher is preferably 0.1 to 100% by weight, more preferably 0.2 to 80% by weight, and particularly preferably 0. .3 to 50% by weight. When the ratio of the eluted components is within the above range, the stereoregularity of the propylene-based polymer is sufficiently high, and the mechanical properties such as heat resistance and flexural modulus of the propylene-based polymer are improved.

<Requirement (7)>
The propylene-based polymer of the present invention has a ^{mesopentad fraction (mm mm) determined by 13} C-NMR, preferably 99.4 to 100%, more preferably 99.45 to 99.99%, and particularly preferably 99. It is 5 to 99.95%. When the mesopentad fraction is within the above range, the stereoregularity of the propylene-based polymer tends to be sufficiently high.

Here, the mesopentad fraction indicates the abundance ratio of the quintuplet isotactic structure in the molecular chain, and the fraction of the propylene structural unit at the center of the chain in which five propylene monomer units have a continuous meso structure. The rate. The mesopentad fraction can be determined by the method described in Examples described later.

[Catalyst for olefin polymerization]
The catalyst for olefin polymerization that can be used in the present invention is not particularly limited as long as the above-mentioned propylene-based polymer of the present invention can be obtained, but for example,
(I) A solid titanium catalyst component containing magnesium, titanium, halogen and an electron donor and satisfying the following requirements (k1) to (k4).
(Ii) The organosilicon compound component represented by the following formula (II) and
(Iii) A catalyst [A] containing an organometallic compound component containing an element belonging to Group 1, Group 2, or Group 13 of the Periodic Table, or
A catalyst [B] containing a prepolymerization catalyst (p) in which propylene is prepolymerized on the catalyst [A], the organosilicon compound component (ii), and the organometallic compound component (iii).
Can be mentioned.

(K1) The titanium content is 2.5% by weight or less.

(K2) The content of the electron donor is 8 to 30% by weight.

(K3) The electron donor / titanium (weight ratio) is 7 or more.

(K4) Titanium is not substantially desorbed by hexane washing at room temperature.

R ¹ Si (OR ² ) ₂ (NR ³ R ⁴ ) ・ ・ ・ (II)
In formula (II), R ¹ represents a secondary or tertiary hydrocarbon group having 1 to 20 carbon atoms, R ² represents a hydrocarbon group having 1 to 4 carbon atoms, and R ³ represents a hydrocarbon group having 1 to 12 carbon atoms. Indicates a hydrocarbon group or a hydrogen atom of, and R ⁴ indicates a hydrocarbon group having 1 to 12 carbon atoms.

Hereinafter, each component constituting the olefin polymerization catalyst will be described.

<Solid titanium catalyst component (i)>
The solid titanium catalyst component (i) is
(A) Solid titanium, which contains magnesium, titanium, halogen and electron donors, and titanium is not desorbed by hexane washing at room temperature.
(B) Aromatic hydrocarbons,
It can be prepared by a method including (c) contacting liquid titanium and (d) an electron donor.

≪ (a) Solid titanium ≫
The solid titanium (a) is a known method for preparing a solid titanium catalyst component by contacting a magnesium compound, a titanium compound, an electron donor (internal donor), or the like by various methods (for example, JP-A-4-096111). No., JP-A-58-83006, JP-A-8-143580, etc.).

The magnesium compound is preferably used in a solid state. The magnesium compound in the solid state may be the magnesium compound itself in the solid state, or may be an adduct with an electron donor. Examples of the magnesium compound include magnesium compounds described in JP-A-2004-2742, specifically, magnesium chloride, ethoxymagnesium chloride, butoxymagnesium and the like. Examples of the electron donor include compounds having a magnesium compound solubilizing ability described in JP-A-2004-2742, specifically, alcohols, aldehydes, amines, carboxylic acids, and mixtures thereof. The amount of the magnesium compound and electron donor used varies depending on the type, contact conditions, etc., but 0.1 to 20 mol / liter, preferably 0.5 to 20 mol / liter of the magnesium compound with respect to the liquid electron donor. It can be used in an amount of 5 mol / liter.

The titanium compound is preferably used in a liquid state. Examples of such a titanium compound include a tetravalent titanium compound represented by the following formula (III).

Ti (OR ⁵ ) _g X _4-g・ ・ ・ (III)
In formula (III), R ⁵ is a hydrocarbon group, X is a halogen atom, and 0 ≦ g ≦ 4.

As the titanium compound, titanium tetrachloride is particularly preferable. Further, the titanium compound may be used in combination of two or more kinds.

Examples of the electron donor (internal donor) include a compound represented by the following formula (IV) (hereinafter, also referred to as “compound (IV)”).

式（IV）中、Ｒは、炭素原子数１〜１０、好ましくは２〜８、より好ましくは３〜６の直鎖状もしくは分岐状のアルキル基を示し、Ｒ'は炭素数１〜１０の直鎖状もしくは分岐状のアルキル基を示し、ｎは０〜４の整数を示す。本発明では、ｎが０の化合物が好ましい。

In formula (IV), R represents a linear or branched alkyl group having 1 to 10 carbon atoms, preferably 2 to 8, more preferably 3 to 6, and R'has 1 to 10 carbon atoms. It represents a linear or branched alkyl group, where n is an integer from 0 to 4. In the present invention, a compound having n of 0 is preferable.

Examples of alkyl groups of R and R'are methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, tert-butyl group, pentyl group, hexyl group and heptyl. Examples include a group, an octyl group, a nonyl group, and a decyl group.

Specific examples of the compound (IV) include dimethyl phthalate, methyl ethyl phthalate, diethyl phthalate, n-propyl phthalate, diisopropyl phthalate, di-butyl phthalate, diisobutyl phthalate, and di-n-phthalate. Pentyl, dineopentyl phthalate, di n-hexyl phthalate, di n-heptyl phthalate, di (methylhexyl) phthalate, di (dimethylpentyl) phthalate, di (ethylpentyl) phthalate, di (2, phthalate) 2,3-trimethylbutyl), din-octyl phthalate, di-2-ethylhexyl phthalate and the like. Of these, diisobutyl phthalate is particularly preferred.

In the present invention, another electron donor other than the compound (IV) may be used as the electron donor (internal donor). As another electron donor, for example, a compound having two or more ether bonds existing via a plurality of atoms (hereinafter, also referred to as “polyether compound”) can be mentioned.

Examples of the polyether compound include compounds in which the atoms existing between the ether bonds are carbon, silicon, oxygen, nitrogen, sulfur, phosphorus, boron, or two or more kinds of atoms selected from these. .. Of these, a compound in which a relatively bulky substituent is bonded to the atom between the ether bonds and a plurality of carbon atoms are contained in the atom existing between two or more ether bonds is preferable. For example, a polyether compound represented by the following formula (3) is preferable.

前記式（３）において、ｍは１〜１０の整数、好ましくは３〜１０の整数、より好ましくは３〜５の整数である。Ｒ¹¹、Ｒ¹²、Ｒ³¹〜Ｒ³⁶は、それぞれ独立に、水素原子、または炭素、水素、酸素、フッ素、塩素、臭素、ヨウ素、窒素、硫黄、リン、ホウ素およびケイ素から選択される少なくとも１種の元素を有する置換基である。Ｒ¹¹およびＲ¹²は、それぞれ独立に、好ましくは炭素原子数１〜１０の炭化水素基であり、より好ましくは炭素原子数２〜６の炭化水素基である。Ｒ³¹〜Ｒ³⁶は、それぞれ独立に、好ましくは水素原子または炭素原子数１〜６の炭化水素基である。

In the above formula (3), m is an integer of 1 to 10, preferably an integer of 3 to 10, and more preferably an integer of 3 to 5. R ¹¹ , R ¹² , R ^{31 to} R ³⁶ are each independently selected from a hydrogen atom or at least one selected from carbon, hydrogen, oxygen, fluorine, chlorine, bromine, iodine, nitrogen, sulfur, phosphorus, boron and silicon. It is a substituent having a seed element. R ¹¹ and R ¹² are each independently, preferably a hydrocarbon group having 1 to 10 carbon atoms, and more preferably a hydrocarbon group having 2 to 6 carbon atoms. R ^{31 to} R ³⁶ are each independently, preferably a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.

Specific examples of R ¹¹ and R ¹² include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, isopentyl group, neopentyl group, hexyl group, heptyl group, octyl group, 2 -Ethylhexyl group, decyl group, cyclopentyl group, cyclohexyl group can be mentioned. Among these, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group and an isobutyl group are preferable. Specific examples of R ^{31 to} R ³⁶ include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an isobutyl group. Among these, a hydrogen atom and a methyl group are preferable. Any R ¹¹ , R ¹² , R ^{31 to} R ³⁶ (preferably R ¹¹ , R ¹² ) may jointly form a ring other than the benzene ring, and the main chain contains an atom other than carbon. It may be.

Specific examples of the polyether compound include 2,2-dicyclohexyl-1,3-dimethoxypropane, 2,2-diethyl-1,3-dimethoxypropane, and 2,2-dipropyl-1,3-dimethoxypropane, 2. , 2-Dibutyl-1,3-dimethoxypropane, 2-methyl-2-propyl-1,3-dimethoxypropane, 2-methyl-2-ethyl-1,3-dimethoxypropane, 2-methyl-2-isopropyl- 1,3-Dimethoxypropane, 2-methyl-2-cyclohexyl-1,3-dimethoxypropane, 2,2-bis (2-cyclohexylethyl) -1,3-dimethoxypropane, 2-methyl-2-isobutyl-1 , 3-Dimethoxypropane, 2-methyl-2- (2-ethylhexyl) -1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2,2-bis (cyclohexylmethyl) -1, 3-Dimethoxypropane, 2,2-diisobutyl-1,3-diethoxypropane, 2,2-diisobutyl-1,3-dibutoxypropane, 2-isobutyl-2-isopropyl-1,3-dimethoxypropane, 2, 2-Di-s-butyl-1,3-dimethoxypropane, 2,2-di-t-butyl-1,3-dimethoxypropane, 2,2-dineopentyl-1,3-dimethoxypropane, 2-isopropyl-2 -Isopentyl-1,3-dimethoxypropane, 2-cyclohexyl-2-cyclohexylmethyl-1,3-dimethoxypropane, 2,3-dicyclohexyl-1,4-diethoxybutane, 2,3-diisopropyl-1,4- Diethoxybutane, 2,4-diisopropyl-1,5-dimethoxypentane, 2,4-diisobutyl-1,5-dimethoxypentane, 2,4-diisoamyl-1,5-dimethoxypentane, 3-methoxymethyl tetrahydrofuran, 3 −methoxymethyldioxane, 1,2-diisobutoxypropane, 1,2-diisobutoxyethane, 1,3-diisoamyloxyethane, 1,3-diisoamyloxypropane, 1,3-diisoneopentyroxy Ethane, 1,3-dineopentyroxypropane, 2,2-tetramethylene-1,3-dimethoxypropane, 2,2-pentamethylene-1,3-dimethoxypropane, 2,2-hexamethylene-1,3 -Dimethoxypropane, 1,2-bis (methoxymethyl) cyclohexane, 2-cyclohexyl-2-ethoxymethyl-1,3-di Ethoxypropane, 2-cyclohexyl-2-methoxymethyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxycyclohexane, 2-isopropyl-2-isoamyl-1,3-dimethoxycyclohexane, 2-cyclohexyl -2-methoxymethyl-1,3-dimethoxycyclohexane, 2-isopropyl-2-methoxymethyl-1,3-dimethoxycyclohexane, 2-isobutyl-2-methoxymethyl-1,3-dimethoxycyclohexane, 2-cyclohexyl-2 -Ethoxymethyl-1,3-diethoxycyclohexane, 2-cyclohexyl-2-ethoxymethyl-1,3-dimethoxycyclohexane, 2-isopropyl-2-ethoxymethyl-1,3-diethoxycyclohexane, 2-isopropyl-2 Examples thereof include −ethoxymethyl-1,3-dimethoxycyclohexane, 2-isobutyl-2-ethoxymethyl-1,3-diethoxycyclohexane, 2-isobutyl-2-ethoxymethyl-1,3-dimethoxycyclohexane and the like. ..

Among these, 1,3-diethers are preferable, 2-isopropyl-2-isobutyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl- More preferably, 1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, and 2,2-bis (cyclohexylmethyl) 1,3-dimethoxypropane. One of these compounds may be used, or two or more of these compounds may be used in combination.

<< Preparation of solid titanium (a) >>
The solid titanium (a) can be prepared by contacting the magnesium compound, the titanium compound, and the electron donor. At this time, it is preferable to suspend the magnesium compound in a solid state in a hydrocarbon solvent for use. Further, when the respective components are brought into contact with each other, the liquid titanium compound may be used once to generate the solid substance (1), and the obtained solid substance (1) is further contacted with the liquid titanium compound. It may be allowed to generate a solid substance (2). Further, it is preferable to wash the solid (1) or (2) with a hydrocarbon solvent, if necessary, and then prepare the solid titanium (a).

The contact of each component as described above is usually carried out at a temperature of −70 ° C. to + 200 ° C., preferably −50 ° C. to + 150 ° C., more preferably −30 ° C. to + 130 ° C. The amount of each component used in preparing the solid titanium (a) varies depending on the preparation method and cannot be unconditionally specified. For example, the electron donor is 0.01 to 10 mol, preferably 0 per mol of the magnesium compound. In an amount of .1-5 mol, the titanium compound can be used in an amount of 0.01-1000 mol, preferably 0.1-200 mol.

In the present invention, the solid (1) or (2) thus obtained can be used as it is as the solid titanium (i), and the solid is washed with a hydrocarbon solvent at 0 to 150 ° C. Is preferable.

Examples of the hydrocarbon solvent include aliphatic hydrocarbon solvents such as hexane, heptane, octane, nonane, decane and cetan, non-halogen aromatic hydrocarbon solvents such as toluene, xylene and benzene, and halogen-containing aromatic solvents. A hydrocarbon solvent or the like is used. Of these, an aliphatic hydrocarbon solvent or a halogen-free aromatic hydrocarbon solvent is preferably used.

When cleaning the solid matter, the hydrocarbon solvent is usually used in an amount of 10 to 500 ml, preferably 20 to 100 ml per 1 g of the solid matter. The solid titanium (a) thus obtained contains magnesium, titanium, halogen and an electron donor. In this solid titanium (a), the electron donor / titanium (weight ratio) is preferably 6 or less.

The solid titanium (a) thus obtained is not desorbed by hexane washing at room temperature.

≪ (b) Aromatic hydrocarbons ≫
Examples of the aromatic hydrocarbon (b) used for contact with the solid titanium (a) include benzene, toluene, xylene, ethylbenzene, and halogen-containing hydrocarbons thereof. Of these, xylene (particularly paraxylene) is preferred. By contacting the solid titanium (a) with such an aromatic hydrocarbon (b), it is possible to reduce the so-called "surplus titanium compound" that by-produces a low stereoregular component.

≪ (c) Liquid titanium ≫
Examples of the liquid titanium (c) used for contact with the solid titanium (a) include those similar to the titanium compound used when preparing the solid titanium (a). Among them, titanium tetrahalogenate is preferable, and titanium tetrachloride is particularly preferable.

≪ (d) Electron donor ≫
Examples of the electron donor (d) used for contact with the solid titanium (a) include the same as those exemplified in the above-mentioned electron donor (internal donor). Among them, it is preferable to use the same electron donor used for the preparation of the solid titanium (a).

<< Preparation method of solid titanium catalyst component (i) >>
The contact of the solid titanium (a), the aromatic hydrocarbon (b), the liquid titanium (c) and the electron donor (d) is usually at a temperature of 110 to 160 ° C, preferably 115 ° C to 150 ° C for 1 minute. It is carried out for 10 hours, preferably 10 minutes to 5 hours.

In this contact, the aromatic hydrocarbon (b) is used in an amount of usually 1 to 10000 ml, preferably 5 to 5000 ml, more preferably 10 to 1000 ml per 1 g of solid titanium (a). The liquid titanium (c) is usually used in the range of 0.1 to 50 ml, preferably 0.2 to 20 ml, particularly preferably 0.3 to 10 ml with respect to 100 ml of the aromatic hydrocarbon (b). The electron donor (d) is usually used in an amount of 0.01 to 10 ml, preferably 0.02 to 5 ml, particularly preferably 0.03 to 3 ml with respect to 100 ml of the aromatic hydrocarbon (b).

The contact order of the solid titanium (a), the aromatic hydrocarbon (b), the liquid titanium (c) and the electron donor (d) is not particularly limited, and the solid titanium (a), the aromatic hydrocarbon (b), and the electron donor (d) can be contacted simultaneously or sequentially.

It is preferable that the solid titanium (a), the aromatic hydrocarbon (b), the liquid titanium (c) and the electron donor (d) are brought into contact with each other under an inert gas atmosphere and stirring. For example, in a fully nitrogen-substituted glass flask with a stirrer, a slurry of solid titanium (a), aromatic hydrocarbons (b), liquid titanium (c) and electron donor (d) is placed at the above temperatures. , Stirring the stirrer at 100-1000 rpm, preferably 200-800 rpm for the above time to stir solid titanium (a), aromatic hydrocarbons (b), liquid titanium (c) and electron donors ( It is desirable to bring d) into contact.

The solid titanium (a) and the aromatic hydrocarbon (b) after contact can be separated by filtration.

By such contact between the solid titanium (a) and the aromatic hydrocarbon (b), the solid titanium catalyst component (i) having a lower titanium content than the solid titanium (a) can be obtained. Specifically, the solid titanium catalyst component (i) having a titanium content of 25% by weight or more, preferably 30 to 95% by weight, preferably 40 to 90% by weight less than that of the solid titanium (a) can be obtained.

The solid titanium catalyst component (i) obtained as described above contains magnesium, titanium, halogen and an electron donor, and satisfies the following requirements (k1) to (k4), preferably the following requirements (k5). Is further satisfied.

(K1) The titanium content of the solid titanium catalyst component (i) is 2.5% by weight or less, preferably 2.2 to 0.1% by weight, more preferably 2.0 to 0.2% by weight, and particularly preferably. Is 1.8 to 0.3% by weight, most preferably 1.5 to 0.4% by weight.

The content of the (k2) electron donor is 8 to 30% by weight, preferably 9 to 25% by weight, and more preferably 10 to 20% by weight.

(K3) The electron donor / titanium (weight ratio) is 7 or more, preferably 7.5 to 35, more preferably 8 to 30, and particularly preferably 8.5 to 25.

(K4) The solid titanium catalyst component (i) is substantially free of titanium by hexane washing at room temperature. The hexane cleaning of the solid titanium catalyst component (i) means that 1 g of the solid titanium catalyst component (i) is washed with hexane in an amount of usually 10 to 500 ml, preferably 20 to 100 ml for 5 minutes. Say. Room temperature is 15 to 25 ° C. Further, the fact that titanium is not substantially desorbed means that the titanium concentration in the hexane cleaning solution is 0.1 g / liter or less.

The solid titanium catalyst component (i) has an average particle size of 5 to 70 μm, preferably 7 to 65 μm, more preferably 8 to 60 μm, and particularly preferably 10 to 55 μm.

Here, the amounts of magnesium, halogen, titanium and electron donor are each% by weight per unit weight of the solid titanium catalyst component (i), and magnesium, halogen and titanium are obtained by plasma emission spectroscopy (ICP method). , Electron donors are quantified by gas chromatography. The average particle size of the catalyst is measured by a centrifugal sedimentation method using a decalin solvent.

When the solid titanium catalyst component (i) as described above is used as a catalyst component for olefin polymerization, propylene can be polymerized with high activity, and the amount of polypropylene having low stereoregularity is small, resulting in high stereoregularity. Sexual polypropylene can be stably produced.

<Organosilicon compound component (ii)>
The organosilicon compound component (ii) constituting the catalyst for olefin polymerization of the present invention is represented by the following formula (II).

R ¹ Si (OR ² ) ₂ (NR ³ R ⁴ ) ・ ・ ・ (II)
In formula (II), R ¹ represents a secondary or tertiary hydrocarbon group having 1 to 20 carbon atoms, R ² represents a hydrocarbon group having 1 to 4 carbon atoms, and R ³ represents a hydrocarbon group having 1 to 12 carbon atoms. Indicates a hydrocarbon group or a hydrogen atom of, and R ⁴ indicates a hydrocarbon group having 1 to 12 carbon atoms.

Examples of R ¹ include an alicyclic hydrocarbon group, for example, a cyclobutyl group, a cyclopentyl group, a cyclopentenyl group, a cyclopentadienyl group, a cyclohexyl group, a cyclohexynyl group, these groups having a substituent and the like.

Further, as R ¹ , examples of the hydrocarbon group in which the carbon adjacent to Si is a secondary carbon include an i-propyl group, an s-butyl group, an s-amyl group, an α-methylbenzyl group, and the like. Examples of the hydrocarbon group in which the adjacent carbon is a tertiary carbon include a tert-butyl group, a tert-amyl group, an α, α'-dimethylbenzyl group, an admantyl group and the like.

Among these, a cyclopentyl group and a cyclobutyl group are preferable, and a cyclopentyl group is particularly preferable.

The R ^2, for example, a methyl group, an ethyl group, n- propyl group, iso- propyl, n- butyl, iso- butyl group, ter t - butyl group, etc. sec- butyl group. Of these, methyl and ethyl groups are particularly preferred.

The R ^3, for example, hydrogen, methyl group, ethyl group, n- propyl group, iso- propyl, n- butyl, iso- butyl group, ter t - butyl group, sec- butyl group, n- pentyl group , Iso-pentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, octyl group and the like. Of these, the ethyl group is particularly preferred.

The R ^4, for example, a methyl group, an ethyl group, n- propyl group, iso- propyl, n- butyl, iso- butyl group, ter t - butyl group, sec- butyl group, n- pentyl group, iso -Pentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, octyl group and the like can be mentioned. Of these, the ethyl group is particularly preferred.

Specific examples of the organosilicon compound represented by the above formula (II) include cyclopentyldiethylaminodimethoxysilane, cyclopentenyldiethylaminodimethoxysilane, cyclopentadienyldiethylaminodimethoxysilane, cyclohexyldiethylaminodimethoxysilane, isopropyldiethylaminodimethoxysilane, and tert-butyldiethylamino. Examples thereof include dimethoxysilane.

Among the organosilicon compounds represented by the formula (II), cyclopentyldiethylaminodimethoxysilane is preferable from the viewpoint of increasing the high stereoregularity, particularly the long mesochain length and the high temperature elution amount ratio of TREF.

The above-mentioned organosilicon compound component (ii) may be used alone or in combination of two or more.

By using the solid titanium catalyst component (i) and the organosilicon compound component (ii) in combination, a propylene-based polymer having an unprecedented level of high stereoregularity can be obtained.

<Organometallic compound component (iii)>
The organometallic compound component (iii) constituting the olefin polymerization catalyst of the present invention is an organometallic compound containing a metal belonging to Group 1, Group 2, or Group 13 of the periodic table, and is, for example, an organoaluminum compound, the first. Examples thereof include a complex alkyl compound of a group metal and aluminum, an organometallic compound of a group 2 metal, and the like. Two or more kinds of organometallic compound component (iii) may be used in combination.

≪Organoaluminium compound≫
The organoaluminum compound is represented by, for example, the following formula.

R ^a _n AlX _3-n
In the formula, ^Ra is a hydrocarbon group having 1 to 12 carbon atoms, X is a halogen or hydrogen, and n is 1 to 3.

^Ra is a hydrocarbon group having 1 to 12 carbon atoms, for example, an alkyl group, a cycloalkyl group or an aryl group, and specifically, methyl, ethyl, n-propyl, isopropyl, isobutyl, pentyl, hexyl, etc. Octyl, cyclopentyl group, cyclohexyl, phenyl, trill and the like.

Further, as the organoaluminum compound, a compound represented by the following formula can also be mentioned.

R ^a _n AlY _3-n
In the formula, R ^a is the same as above, Y is -OR ^b group, -OSiR ^c ₃ ^{group, -OAlR d} ₂ group, -NR ^e ₂ group, -SiR ^f ₃ group or -N (R ^g ) AlR. ^{h is} ₂ groups, n is 1 to 2, R ^b , R ^c , R ^d and R ^h are methyl group, ethyl group, isopropyl group, isobutyl group, cyclohexyl group, phenyl group and the like, and R ^e is Hydrogen, methyl group, ethyl group, isopropyl group, phenyl group, trimethylsilyl group and the like, and R ^f and R ^g are methyl group, ethyl group and the like.

Specific examples of such organoaluminum compounds include the following compounds.
_{^{· R a n Al (OR b}} ) a compound represented by _3-n, e.g., dimethylaluminum methoxide, diethylaluminum ethoxide and diisobutylaluminum methoxide.
_{^{· R a n Al (OSiR c}} ) a compound represented by _3-n, e.g., _{Et 2 Al (OSiMe 3),} (iso-Bu) 2 Al (OSiMe 3), (iso-Bu) 2 Al (OSiEt 3) Such.
_{^{· R a n Al (OAlR d}} 2) 3-n Et 2 AlOAlEt 2, such as _{(iso-Bu) 2 AlOAl (} iso-Bu) 2.

Among the above-mentioned organoaluminum compounds, the organoaluminum compound ^{represented by Ra} ₃ Al is preferably used.

[Method for producing catalyst for olefin polymerization]
The olefin polymerization catalyst can be produced by a method including a step of contacting the solid titanium catalyst component (i), the organosilicon compound component (ii), and the organometallic compound component (iii). ..

In the present invention, when forming a catalyst for olefin polymerization from each of these components (i), (ii), and (iii), other components can be used if necessary.

In the present invention, the prepolymerization catalyst (p) may be formed from each of the above components. The prepolymerization catalyst (p) is formed by prepolymerizing propylene in the presence of the above-mentioned components (i), (ii), (iii) and other components used as needed. Such a prepolymerization catalyst (p) usually forms a catalyst for olefin polymerization together with the organic silicon compound (ii) and the organic metal compound (iii), but only the prepolymerization catalyst (p) is used as the catalyst for olefin polymerization. In some cases it can be done.

[Method for producing propylene polymer]
In the method for producing a propylene-based polymer of the present invention, propylene is polymerized in the presence of the above-mentioned olefin polymerization catalyst.

When polymerizing propylene, in addition to propylene, a small amount of other olefins other than propylene or a small amount of diene compound may coexist in the polymerization system to produce a random copolymer. Examples of such olefins other than propylene include ethylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, and 3-methyl-. Examples thereof include olefins having 2 to 8 carbon atoms such as 1-butene. Of these, ethylene is preferred. In the case of the random copolymer, the content of the comonomer other than propylene is preferably 6 mol% or less, more preferably 3 mol% or less.

In the present invention, the polymerization can be carried out by either a liquid phase polymerization method such as solution polymerization or suspension polymerization or a gas phase polymerization method. When the polymerization takes the reaction form of slurry polymerization, an inert organic solvent can be used as the reaction solvent, or a liquid olefin at the reaction temperature can be used.

Specific examples of the inert organic solvent include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; alicyclic hydrocarbons; aromatic hydrocarbons; halogenated hydrocarbons. Examples thereof include hydrogen and contact materials thereof. Among these, it is particularly preferable to use an aliphatic hydrocarbon.

During polymerization, the solid titanium catalyst component (i) or prepolymerization catalyst (p) is usually about 1 × 10 ^-5 to 1 mmol, preferably about 1 ×, in terms of titanium atoms per liter of polymerization volume. It is used in an amount of ^{10-4 to 0.1 mmol.}

The organosilicon compound (ii) is usually used in an amount of about 0.001 mol to 10 mol, preferably 0.01 mol to 5 mol, based on 1 mol of the metal atom of the organometallic compound (iii).

The organometallic compound (iii) is used in an amount such that the metal atom in the compound (iii) is usually about 1 to 2000 mol, preferably about 2 to 500 mol, with respect to 1 mol of the titanium atom in the polymerization system. Be done.

If the prepolymerization catalyst (p) is used during this polymerization, it may not be necessary to add the organosilicon compound (ii) and / or the organometallic compound (iii). When the catalyst for olefin polymerization is formed from the prepolymerization catalyst (p), the component (ii) and the component (iii), each of these components (ii) and (iii) can be used in the above amounts.

If hydrogen is used at the time of polymerization, the molecular weight of the obtained propylene polymer can be adjusted, and a polymer having a large MFR can be obtained.

In the present invention, the polymerization is usually carried out at a temperature of about 20 to 150 ° C., preferably about 50 to 100 ° C., and under a pressure of ^{normal pressure to 100 kg / cm 2} , preferably about 2 to 50 kg / cm ^2. ..

In the present invention, the polymerization can be carried out by any of a batch method, a semi-continuous method and a continuous method. Further, the polymerization can be carried out in two or more stages by changing the reaction conditions. Further, in the present invention, a homopolymer of propylene may be produced, or a random copolymer, a block copolymer or the like may be produced from an olefin other than propylene.

[Propylene resin composition]
The propylene-based resin composition of the present invention is a resin composition containing the above-mentioned propylene-based polymer of the present invention (hereinafter, also referred to as “propylene-based polymer (A)”) as an essential constituent component. The components other than the propylene-based polymer (A) constituting the propylene-based resin composition of the present invention are not particularly limited, and known components can be blended depending on the intended use.

A preferred embodiment of the propylene-based resin composition of the present invention is
20 to 80% by mass of a propylene-based block copolymer (C) composed of a propylene homopolymer portion and a propylene / α-olefin copolymer portion,
Ethylene-α-olefin copolymers (D) 1 to 50 containing 50 to 95 mol% of a structural unit derived from ethylene and 5 to 50 mol% of a structural unit derived from an α-olefin having 3 to 20 carbon atoms. Mass% and Inorganic Filler (E) 0-70 Mass%
(However, the total of the components (C), (D) and (E) is 100% by mass).
The propylene-based block copolymer (C) is converted into propylene as the propylene homopolymer portion, 60 to 99% by mass of the propylene-based polymer (A), and as the propylene / α-olefin copolymer portion. Propylene / α-olefin copolymer (B) 1 to contain a constituent unit of 55 to 90 mol% derived from the constituent unit and a constituent unit of 10 to 45 mol% derived from an α-olefin having 2 to 20 carbon atoms other than propylene. Including 40% by mass (however, the total of the components (A) and (B) is 100% by mass).
Propylene-based resin composition (hereinafter, also referred to as "first composition");
A propylene-based resin composition containing 100 parts by mass of the propylene-based polymer (A) and 0.01 to 10 parts by mass of the nucleating agent (F) (hereinafter, also referred to as "second composition");
70 to 99.5% by mass of at least one component selected from the group consisting of the propylene-based polymer (A) and the propylene-based block copolymer (C).
A propylene-based resin composition containing 0.5 to 30% by mass of an inorganic fiber (G) (however, the total of the components (A), (C) and (G) is 100% by mass) (hereinafter, "third". Also referred to as "composition of")
And so on. Hereinafter, each composition will be described.

<First composition>
The first composition of the present invention is a resin containing the propylene-based block copolymer (C) and the ethylene / α-olefin copolymer (D), and further containing an inorganic filler (E), if necessary. It is a composition, and the propylene-based block copolymer (C) contains the propylene-based polymer (A) and the propylene / α-olefin copolymer (B). Such a first composition of the present invention can form a molded product having excellent fluidity during molding and excellent flexural modulus and impact resistance.

In the first composition of the present invention, a propylene homopolymer is used as the propylene-based polymer (A) constituting the propylene-based block copolymer (C).

In the first composition of the present invention, the propylene-based polymer (A) and the propylene / α-olefin copolymer (B) are mixed to form a propylene-based block copolymer (C), and then the propylene-based block copolymer (C) is formed. It can be prepared by mixing the ethylene / α-olefin copolymer (D) and, if necessary, the inorganic filler (E).

≪Propene block copolymerization, etc. (C) ≫
The propylene-based block copolymer (C) contains 60 to 99% by mass, preferably 70 to 97% by mass, and more preferably 75 to 95% by mass of the propylene-based polymer (A) as a propylene homopolymer portion. The propylene / α-olefin copolymer (B) is contained in the range of 1 to 40% by mass, preferably 3 to 30% by mass, and more preferably 5 to 25% by mass (however, the component (A)). And (B) are 100% by mass.).

By forming the propylene-based block copolymer (C) using the propylene-based polymer (A) and the propylene / α-olefin copolymer (B) in this way, rigidity, heat resistance, and impact resistance are formed. It is possible to form a molded product having an excellent balance with the above.

≪Propene / α-olefin copolymer (B) ≫
The propylene / α-olefin copolymer (B) is a copolymer of propylene and an α-olefin having 2 to 20 carbon atoms other than propylene, and contains 55 to 90 mol% of a constituent unit derived from propylene. It is preferably contained in the range of 60 to 85 mol%, and the constituent unit derived from the α-olefin is contained in the range of 10 to 45 mol%, preferably 15 to 40 mol% (provided that it is derived from propylene). The total of the structural unit and the structural unit derived from the α-olefin is 100 mol%).

Examples of α-olefins having 2 to 20 carbon atoms other than propylene include ethylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, and 3-methyl-1. -Pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like can be mentioned. One of these may be used, or two or more thereof may be used in combination. Of these, ethylene is preferred.

The MFR (ASTM D1238E, measurement temperature 230 ° C., load 2.16 kg) of the propylene / α-olefin copolymer (B) is preferably 0.1 g / 10 minutes or more, more preferably 0.3 to 20 g / 10. Minutes.

The propylene / α-olefin copolymer (B) is produced by various known production methods, for example, by copolymerizing propylene with an α-olefin having 2 to 20 carbon atoms other than propylene in the presence of a metallocene catalyst. can do.

As the propylene / α-olefin copolymer (B), one type may be used, or two or more types may be used in combination.

<< Ethylene / α-olefin copolymer (D) >>
The ethylene / α-olefin copolymer (D) is a random copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms, and has a constituent unit derived from ethylene of 50 to 95 mol%, preferably 55. It is contained in the range of ~ 90 mol%, and the structural unit derived from the α-olefin is contained in the range of 5 to 50 mol%, preferably 10 to 45 mol%. By blending the ethylene / α-olefin copolymer (D) with the propylene-based block copolymer (C), the impact resistance can be further improved.

Examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, and the like. Examples thereof include 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosen. One of these may be used, or two or more thereof may be used in combination. Among these, propylene, 1-butene, 1-hexene and 1-octene are preferable, and 1-butene and 1-octene are more preferable.

The MFR (ASTM D1238E, measurement temperature 230 ° C., load 2.16 kg) of the ethylene / α-olefin copolymer (D) is preferably 0.1 to 50 g / 10 minutes, more preferably 0.3 to 20 g /. It is 10 minutes, more preferably 0.5 to 10 g / 10 minutes. The density of the ethylene / α-olefin copolymer (D) is preferably 0.850 to 0.920 kg / m ³ , and more preferably 0.855 to 0.900 kg / m ³ .

As the ethylene / α-olefin copolymer (D), one produced by a known method may be used, or a commercially available product may be used. Preferred commercial products include, for example, the "Toughmer (registered trademark) A" series and "Toughmer (registered trademark) H" series manufactured by Mitsui Chemicals, Inc., and the "Engage (registered trademark)" series manufactured by DuPont Dow. , ExxonMobil's "Exact®" series and the like.

As the ethylene / α-olefin copolymer (D), one type may be used, or two or more types may be used in combination.

≪Inorganic filler (E) ≫
Examples of the inorganic filler (E) include talc, clay, mica, calcium carbonate, magnesium hydroxide, ammonium phosphate, silicates, carbonates, carbon black, magnesium sulfate fiber, glass fiber, carbon fiber and the like. Can be mentioned. These may be used alone or in combination of two or more. In the first composition of the present invention, it is preferable to use talc as the inorganic filler (E).

Regarding the content of the components (C) to (E) in the first composition of the present invention, when the total of the components (C) to (E) is 100% by mass, the component (C) is 20 to 80. It is mass%, preferably 25 to 75% by mass, more preferably 30 to 70% by mass, and the component (D) is 1 to 50% by mass, preferably 5 to 40% by mass, more preferably 10 to 30% by mass. The component (E) is 0 to 70% by mass, preferably 5 to 60% by mass, and more preferably 10 to 50% by mass.

<Second composition>
The second composition of the present invention is a resin composition containing the propylene-based polymer (A) and the nucleating agent (F), and can form a molded product having excellent rigidity, heat resistance and flexural modulus. it can.

The propylene-based polymer (A) used in the second composition of the present invention may be a propylene homopolymer or a random copolymer containing a monomer other than propylene as a copolymerization component.

Examples of the nucleating agent (F) include sorbitol-based nucleating agents, phosphate-based nucleating agents (organic phosphate metal salts), aromatic carboxylic acid metal salts, aliphatic carboxylic acid metal salts, and rosin-based compounds. Organic nucleating agents; examples thereof include inorganic nucleating agents such as inorganic compounds. One of these may be used, or two or more thereof may be used in combination.

Commercially available products of the nucleating agent (F) include "ADEKA STUB NA-11" (manufactured by ADEKA Corporation), which is a phosphate-based nucleating agent, and "Pine Crystal KM1610" (Arakawa Chemical Co., Ltd.), which is a rosin-based nucleating agent. (Manufactured by), a nuclear agent "Hyperform HPN-20E" (manufactured by Milliken) composed of a metal salt of an aliphatic carboxylic acid, a sorbitol-based nuclear agent "Mirad NX8000" (manufactured by Milliken), and the like.

The content of the nucleating agent (F) in the second composition of the present invention is preferably 0.01 to 10 parts by mass, more preferably 0.05 with respect to 100 parts by mass of the propylene-based polymer (A). ~ 5 parts by mass, more preferably 0.1 to 1.0 parts by mass.

<Third composition>
The second composition of the present invention contains at least one component selected from the group consisting of the propylene-based polymer (A) and the propylene-based block copolymer (C), and the inorganic fiber (G). It is a resin composition, and it is possible to form a molded product having an excellent balance of rigidity, heat resistance and flexural modulus.

The propylene-based polymer (A) used in the third composition of the present invention may be either a propylene homopolymer or a random copolymer, but the propylene-based block copolymer (C) constituting the propylene-based block copolymer (C). The propylene-based polymer (A) is a propylene copolymer.

Examples of the inorganic fiber (G) include magnesium sulfate fiber, glass fiber, carbon fiber and the like. One of these may be used, or two or more thereof may be used in combination.

When magnesium sulfate fibers are used, the average fiber length is preferably 5 to 50 μm, more preferably 10 to 30 μm. The average fiber diameter of the magnesium sulfate fibers is preferably 0.3 to 2 μm, more preferably 0.5 to 1 μm. Examples of commercially available products include "Mosheidi" (manufactured by Ube Material Industries Ltd., trade name).

As the glass fiber, filamentous fiber is obtained by melt-spinning glass such as E glass (Electrical glass), C glass (Chemical glass), A glass (Alkari glass), S glass (High strength glass) and alkali resistant glass. You can list what you have done. The glass fibers are contained in the composition in the form of short fibers of 1 mm or less or long fibers of 1 mm or more.

Examples of the carbon fiber include polyacrylonitrile (PAN) -based carbon fiber made from polyacrylonitrile and pitch-based carbon fiber made from pitch. These carbon fibers can be used as so-called chopped carbon fibers in which the fiber yarn is cut to a desired length, and may be converged with various sizing agents, if necessary. ..

The content of the inorganic fiber (G) in the third composition of the present invention is preferably 1 to 30% by mass, more preferably 2 when the total of the component (A) and the component (G) is 100% by mass. It is ~ 25% by mass, more preferably 5 to 20% by mass.

<Other ingredients>
The propylene-based resin composition of the present invention contains resins, rubbers, fillers, weather-resistant stabilizers, heat-resistant stabilizers, and antistatic agents other than the above-mentioned components (A) to (G), as long as the object of the present invention is not impaired. Other ingredients such as agents, anti-slip agents, anti-blocking agents, anti-fog agents, lubricants, pigments, dyes, plasticizers, anti-aging agents, hydrochloric acid absorbers, antioxidants, crystal nucleating agents and the like can be blended. The blending amount of the other components in the propylene-based resin composition of the present invention is not particularly limited as long as it does not impair the object of the present invention.

<Manufacturing method of propylene resin composition>
The propylene-based resin composition of the present invention can be produced by blending each of the above-mentioned components. Each component may be sequentially blended in any order, or may be mixed at the same time. Further, a multi-step mixing method in which some components are mixed and then other components are mixed may be adopted. However, with respect to the first composition of the present invention, as described above, the propylene-based polymer (A) and the propylene / α-olefin copolymer (B) are mixed to form a propylene-based block copolymer. After forming (C), it is produced by mixing the ethylene / α-olefin copolymer (D) and, if necessary, the inorganic filler (E) and other components. Further, in the case of using the propylene-based block copolymer (C) in the third composition of the present invention, similarly, after forming the propylene-based block copolymer (C) in advance, other components are mixed. Manufactured by

As a method of blending each component, for example, a method of mixing or melt-kneading each component simultaneously or sequentially using a mixing device such as a Banbury mixer, a single-screw extruder, a twin-screw extruder, or a high-speed twin-screw extruder. Can be mentioned.

[Molded product]
The molded product of the present invention is formed by using the above-mentioned propylene-based polymer of the present invention or the propylene-based resin composition of the present invention. Since the propylene-based polymer of the present invention has an unprecedented level of high stereoregularity, high rigidity and high heat resistance, the molded product of the present invention is dimensionally stable with little dimensional change due to temperature changes. Excellent in sex. Therefore, the molded product of the present invention can be suitably used in various fields such as automobile parts, home appliance parts, food containers, and medical containers. Examples of the automobile parts include automobile interior / exterior members such as bumpers and instrumental panels, and outer panel materials such as roofs, door panels, and fenders. In particular, the first composition of the present invention is suitable as an automobile bumper, an instrument panel, a fender, and the second composition of the present invention is suitable as an automobile interior member (for example, a door panel, a pillar, etc.). The third composition of the present invention is suitable as an automobile functional member (for example, engine fan, fan shroud, etc.), but is not limited thereto.

The molding method of the molded product of the present invention is not particularly limited, and various known methods for molding the polymer can be adopted, but injection molding and press molding are particularly preferable.

Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not limited to these Examples. The methods for measuring various physical properties described in the examples are as follows.

<Mesopentad fraction (mmmm (noise removal method))>
1. 1. Measurement condition device: Bruker Biospin AVANCE III cryo-500 type nuclear magnetic resonance device Measurement nucleus: 13C (125MHz)
Measurement mode: Single pulse proton broadband decoupling Pulse width: 45 ° (5.00 microseconds)
Repeat time: 5.5 seconds Accumulation number: 256 times Measurement solvent: o-dichlorobenzene / heavy benzene (80/20% by volume) mixed solvent Sample concentration: 50 mg / 0.6 mL
Measurement temperature: 120 ° C
Chemical shift criteria: 21.59 ppm (mesopentad methyl peak shifts)

2. Calculation method The mesopentad fraction (mmmm,%), which is one of the indexes of the stereoregularity of the polymer and whose microtacticity was examined, is the peak intensity of ^{the 13 C-NMR spectrum obtained under the measurement condition of 1 above.} Calculated from the ratio.
Here, in the case of polypropylene having an unprecedented level of stereoregularity such as the measurement target in the present invention, if the rmrr, mmrm, rmrr, rmrm, and mrrr regions are included in the integral value, the integral of "noise" is included. It is considered that there is a problem that the degree of influence on the value becomes large and S2 in a general calculation method is overestimated, that is, mmmm (%) is underestimated. Even in Prog. Polymer. Sci. 26 (2001), 443-533, in the case of polypropylene having a stereoregularity of 95% or more, if certain requirements are satisfied, the integrated value of the rmrr, mmrm, rmrr, rmrm, and mrrr regions is In theory, it has been reported that the total is 0.1% or less, suggesting that it leads to an overestimation of S2 in a general calculation method.

Therefore, in the present invention, it was calculated according to the following (Equation 1). The rmmer, mmrm, rmrr, rmrm, and rmrr regions were excluded from the calculations as suggested by Prog. Polymer. Sci. 26 (2001), 443-533. Hereinafter, the calculation method in the present specification will be referred to as a "noise removal method".
mmmm (noise removal method) (%) = S1 / S2 * 100 ... (Equation 1)
S1 = (peak containing mmmm, mmml)-(n-propyl end)-(n-butyl end) -mrm * 2
S2 = S1 + mmrr + mmrr + mrrm + rrrrr
= S1 + 5 * mrrm + rrrrr

In the calculation by the above (Equation 1), as an example, it was assigned as follows. It should be noted that the mmm peak overlaps with each of the (n-propyl end) and (n-butyl end) peaks.
Peak including mmmm and mmml: Peak area of 21.2 to 22.0 ppm mmm = mrrm * 2
mmrr = mrrm * 2
mrrm: Peak area of 19.5 to 19.7 ppm rrrr: Peak area of 20.0 to 20.2 ppm n-propyl terminal: (A1 + A3) / 2
A1: Peak area of 14.2ppm A3: Peak area of 39.4ppm n-Butyl end: Peak area of 36.7ppm

<Meso average chain length>
The meso average chain length Ln (m) was calculated based on the following formula.
Ln (m) = 3 + 5X / (1-X)
X = mmmm (noise removal method) (%) / 100

<Measurement of temperature rise elution fractionation (TREF)>
The amount of the TREF high-temperature elution component, which is considered to be one of the indexes of stereoregularity, was calculated from the polymer concentration eluted at 122 ° C. or higher obtained by the temperature rise fractional measurement under the following conditions.
Equipment: Polymer Char CFC2 type cross fractionation chromatograph Detector: Polymer Char IR4 type infrared spectrophotometer (built-in)
Mobile phase: o-dichlorobenzene, BHT added Flow rate: 1.0 mL / min
Sample concentration: 90 mg / 30 mL
Injection volume: 0.5 mL
Dissolution conditions: 145 ° C, 30 min
Stabilization conditions: 135 ° C, 30 min
Temperature drop rate: 1.0 mL / min
Elution classification: -20 ° C to 0 ° C in 10 ° C increments, 0 ° C to 80 ° C in 5 ° C increments,
80 ° C to 104 ° C in 3 ° C increments, 104 to 126 ° C in 2 ° C increments Elution time: 3 min

<Molecular weight distribution>
The Mw / Mn value, which is an index of the molecular weight distribution, was obtained by analyzing a chromatogram measured under the following conditions by a known method.
Equipment: Waters gel permeation chromatograph Alliance GPC2000 type Column: Tosoh TSKgel GMH6-HT x2 + TSKgel GMH6-HTL x2
Mobile phase: o-dichlorobenzene (containing 0.025% BHT)
Flow velocity: 1.0 ml / min
Temperature: 140 ° C
Column calibration: Tosoh monodisperse polystyrene Sample concentration: 0.15% (w / v)
Injection volume: 0.4 ml <Melt flow rate (MFR)>
According to ASTM D1238E, the measurement temperature was 230 ° C.

<Amount of decane-soluble components>
Approximately 6 grams of propylene polymer (this weight is expressed as b (gram) in the formula below), 500 ml of decan, and a small amount of heat-resistant stabilizer soluble in decan are charged in a glass measuring container, and a nitrogen atmosphere is provided. Below, the temperature was raised to 150 ° C. in 2 hours while stirring with a stirrer to dissolve the propylene polymer, and the mixture was held at 150 ° C. for 2 hours and then slowly cooled to 23 ° C. over 8 hours. The liquid containing the precipitate of the obtained propylene polymer was filtered under reduced pressure with a glass filter of 25G-4 standard manufactured by Iwata Glass Co., Ltd. 100 ml of the filtrate was collected and dried under reduced pressure to obtain a part of the decan-soluble component. This weight was expressed as a (gram) in the following formula. After this operation, the amount of decane-soluble component was determined by the following formula.
Decan-soluble component content (% by weight) = 100 x (500 x a) / (100 x b)

<Flexural modulus>
The flexural modulus (MPa) was measured under the following conditions in accordance with ISO 178.
Temperature: 23 ° C
Specimen: 10 mm (width) x 4 mm (thickness) x 80 mm (length)
Bending speed: 2 mm / min Span interval: 64 mm

[Example 1]
<Preparation of solid titanium (a-1)>
After sufficiently replacing a high-speed agitator with an internal volume of 2 liters (manufactured by Tokushu Kagaku Kogyo) with nitrogen, 700 ml of refined kerosene, 10 g of magnesium chloride, 24.2 g of ethanol and sorbitan distearate (manufactured by Kao Atlas Co., Ltd. Emazole 320 ") 3 g was charged. The temperature of this system was raised under stirring, and the mixture was stirred under the conditions of 120 ° C. and 800 rpm for 30 minutes. Under high-speed stirring, the solution was transferred to a 2 liter glass flask (with a stirrer) filled with 1 liter of refined kerosene previously cooled to −10 ° C. using a Teflon (registered trademark) tube having an inner diameter of 5 mm. The obtained solid was filtered and thoroughly washed with purified n-hexane to obtain a solid adduct in which 2.8 mol of ethanol was coordinated with 1 mol of magnesium chloride.

Then, the solid adduct (45 mmol in terms of magnesium atom) was suspended in 20 ml of decane, and then the whole amount was introduced into 195 ml of titanium tetrachloride kept at −20 ° C. under stirring. The mixture was heated to 80 ° C. over 5 hours and 1.8 ml (6.2 mmol) of diisobutylphthalate was added. The temperature was subsequently raised to 110 ° C. and the mixture was stirred for 1.5 hours.

After completion of the reaction for 1.5 hours, the solid part was collected by hot filtration and washed with decan at 100 ° C. and hexane at room temperature until titanium was no longer detected in the filtrate. In this way, solid titanium (a-1) containing 3.8% by weight of titanium, 16% by weight of magnesium, 18.2% by weight of diisobutylphthalate, and 1.1% by weight of etanol residues was obtained. Obtained.

<Preparation of solid titanium catalyst component (i-1)>
In a 200 ml glass reactor fully nitrogen-substituted, 6.8 g of the obtained solid titanium (a-1), 113 ml of para-xylene, 11 ml of decane, 2.5 ml (23 mmol) of titanium tetrachloride and diisobutylphthale -To 0.34 ml (1.2 mmol) was added. The temperature inside the reactor was raised to 130 ° C., and the mixture was stirred at that temperature for 1 hour for contact treatment, and then the solid part was collected by thermal filtration. This solid portion was resuspended in 101 ml of para-xylene, and 1.7 ml (15 mmol) of titanium tetrachloride and 0.22 ml (0.8 mmol) of diisobutylphthalate were further added.

Then, the temperature was raised to 130 ° C., and the mixture was stirred and reacted for 1 hour while maintaining the temperature. After completion of the reaction, solid-liquid separation was performed again by hot filtration, and the obtained solid part was washed with decane at 100 ° C. and hexane at room temperature until the amount of para-xylene in the catalyst was 1% by weight or less. In this way, a solid titanium catalyst component (i-1) containing 1.3% by weight of titanium, 20% by weight of magnesium, and 13.8% by weight of diisobutylphthalate was obtained.

<Main polymerization>
In a 30 ml glass container containing 7 ml of heptane, 0.35 mmol of triethylaluminum, 0.07 mmol of cyclopentyldiethylaminodimethoxysilane, and 0.0028 of the obtained solid titanium catalyst component (i-1) in terms of titanium atom. A catalyst for olefin polymerization was prepared by charging in mmol and contacting at 20 ° C. for 10 minutes. Next, the catalyst for olefin polymerization was charged into an autoclave having an internal volume of 2 liters charged with 500 g of propylene, and polymerization was carried out at 20 ° C. for 10 minutes, and then 10 liters of hydrogen was further charged into the system. The temperature was raised to 70 ° C. and polymerization was carried out for 1 hour. Then, the polymerization was stopped by adding ethanol, and unreacted propylene was purged to obtain 371 g of polypropylene (A-1). Table 1 shows the results of evaluating the physical characteristics of the obtained polypropylene (A-1).

[Example 2]
In Example 1, the same procedure as in Example 1 was carried out except that the hydrogen charged in the main polymerization was changed from 10 liters to 7.5 liters. Table 1 shows the results of evaluating the physical characteristics of the obtained polypropylene (A-2).

[Example 3]
<Main polymerization>
In a 30 ml glass container containing 7 ml of heptane, 0.35 mmol of triethylaluminum, 0.07 mmol of cyclopentyldiethylaminodimethoxysilane, 0.35 mmol of diethylzinc, and Example 1 The solid titanium catalyst component obtained above (Example 1). A-1) was charged in 0.0028 mmol in terms of titanium atom and contacted at 20 ° C. for 10 minutes to prepare a catalyst for olefin polymerization. Next, the catalyst for olefin polymerization was charged into an autoclave having an internal volume of 2 liters charged with 500 g of propylene, and polymerization was carried out at 20 ° C. for 10 minutes, and then 16 liters of hydrogen was further charged into the system. The temperature was raised to 60 ° C. and polymerization was carried out for 1 hour. Then, the polymerization was stopped by adding ethanol, and unreacted propylene was purged to obtain 279 g of polypropylene (A-3). Table 1 shows the results of evaluating the physical characteristics of the obtained polypropylene (A-3).

[Example 4]
In Example 3, the same procedure as in Example 3 was carried out except that the diethylzinc charged in the present polymerization was changed from 0.35 mmol to 0.7 mmol. Table 1 shows the results of evaluating the physical characteristics of the obtained polypropylene (A-4).

[Example 5]
In Example 3, hydrogen charged in the main polymerization was changed from 16 liters to 12.5 liters, and diethylzinc was changed from 0.35 mmol to 2.8 mmol in the same manner as in Example 3. Table 1 shows the results of evaluating the physical characteristics of the obtained polypropylene (A-5).

[Example 6]
<Preparation of prepolymerization catalyst (p-1)>
In a 200 ml glass reactor substituted with nitrogen, 50 ml of hexane, 2.5 mmol of triethylaluminum, 0.5 mmol of cyclopentyldiethylaminodimethoxysilane, and the solid titanium catalyst component (i-1) obtained in Example 1 were placed. After charging 0.25 mmol in terms of titanium atoms, propylene was supplied at an amount of 1.47 liters / hour for 1 hour while keeping the temperature in the system at 20 ° C. By this operation, a prepolymerized catalyst (p-1) in which 3 g of propylene was prepolymerized per 1 g of the solid titanium catalyst component (i-1) was obtained.

<Main polymerization>
500 g of propylene and 7.5 liters of hydrogen were charged into an autoclave having an internal volume of 2 liters, and the temperature inside the system was raised to 60 ° C. Then, 0.7 mmol of triethylaluminum, 0.7 mmol of cyclopentyldiethylaminodimethoxysilane, and 0.0028 mmol of the prepolymerization catalyst (p-1) obtained above were added in terms of titanium atoms to initiate polymerization. .. Polymerization was carried out for 1 hour while maintaining the temperature in the system at 70 ° C. Then, the polymerization was stopped by adding ethanol, and unreacted propylene was purged to obtain 286 g of polypropylene (A-6). Table 1 shows the results of evaluating the physical characteristics of the obtained polypropylene (A-6).

[Example 7]
In Example 6, the same procedure as in Example 6 was carried out except that the charged hydrogen was changed from 7.5 liters to 11.5 liters. Table 1 shows the results of evaluating the physical characteristics of the obtained polypropylene (A-7).

[Comparative Example 1]
In Example 1, the same as in Example 1 except that dicyclopentyl dimethoxysilane was used instead of cyclopentyl diethylaminodimethoxysilane used in the present polymerization and the charged hydrogen was changed from 10 liters to 7.5 liters. went. Table 1 shows the results of evaluating the physical characteristics of the obtained polypropylene (a-1).

[Comparative Example 2]
In Example 1, cyclopentylmethyldimethoxysilane was used instead of cyclopentyldiethylaminodimethoxysilane used in the present polymerization, and the charged hydrogen was changed from 10 liters to 4.5 liters in the same manner as in Example 1. went. Table 1 shows the results of evaluating the physical characteristics of the obtained polypropylene (a-2).

[Comparative Example 3]
In Example 1, the same procedure as in Example 1 was carried out except that diisopropyldimethoxysilane was used instead of cyclopentyldiethylaminodimethoxysilane used in the present polymerization and the charged hydrogen was changed from 10 liters to 4.0 liters. It was. Table 1 shows the results of evaluating the physical characteristics of the obtained polypropylene (a-3).

[Comparative Example 4]
In Example 1, 2-isobutyl-2-isopropyl-1,3-dimethoxypropane was used instead of cyclopentyldiethylaminodimethoxysilane used in this polymerization, and the charged hydrogen was changed from 10 liters to 2.0 liters. Except for what was done, the same procedure as in Example 1 was carried out. Table 1 shows the results of evaluating the physical characteristics of the obtained polypropylene (a-4).

[Comparative Example 5]
<Preparation of solid titanium catalyst component (ci-1)>
95.2 g of anhydrous magnesium chloride, 442 ml of decane and 390.6 g of 2-ethylhexyl alcohol were heated and reacted at 130 ° C. for 2 hours to form a uniform solution, and then 22.2 g of phthalic anhydride was added to this solution. Phthalic anhydride was dissolved by stirring and mixing at 130 ° C. for 1 hour. After cooling the uniform solution thus obtained to room temperature, 75 ml of this uniform solution was added dropwise over 200 ml of titanium tetrachloride kept at −20 ° C. for 1 hour. After completion of charging, the temperature of this mixed solution was raised to 110 ° C. over 4 hours, 5.22 g of diisobutylphthalate was added when the temperature reached 110 ° C., and the mixture was stirred and held at the same temperature for 2 hours. Then, the solid part was collected by heat filtration, the solid part was resuspended in 275 ml of titanium tetrachloride, and then the heating reaction was carried out again at 110 ° C. for 2 hours. After completion of the reaction, the solid part was collected again by hot filtration and washed thoroughly with decane and hexane at 110 ° C. until no free titanium compound was detected in the solution. In this way, a solid titanium catalyst component (ci-1) containing 2.3% by weight of titanium, 20.0% by weight of magnesium, and 10.2% by weight of diisobutylphthalate was obtained.

<Main polymerization>
Except that in Example 1, the solid titanium catalyst component (ci-1) was used instead of the solid titanium catalyst component (i-1), and the charged hydrogen was changed from 10 liters to 6.5 liters. Was carried out in the same manner as in Example 1. Table 1 shows the results of evaluating the physical characteristics of the obtained polypropylene (a-5).

[Comparative Example 6]
In Comparative Example 5, Comparative Example 5 except that dipyrrolidyldimethoxysilane was used instead of cyclopentyldiethylaminodimethoxysilane used in the present polymerization and the charged hydrogen was changed from 6.5 liters to 4.5 liters. I went in the same way. Table 1 shows the results of evaluating the physical characteristics of the obtained polypropylene (a-6).

[Comparative Example 7]
In Example 1, the same as in Example 1 except that diethylaminotriethoxysilane was used instead of cyclopentyldiethylaminodimethoxysilane used in the present polymerization and the charged hydrogen was changed from 10 liters to 1.8 liters. went. Table 1 shows the results of evaluating the physical characteristics of the obtained polypropylene (a-7).

[Comparative Example 8]
In Example 6, Except that diethylaminotriethoxysilane was used instead of cyclopentyldiethylaminodimethoxysilane used in the present polymerization and the charged hydrogen was changed from 7.5 liters to 1.0 liters. It was done in the same way. Table 1 shows the results of evaluating the physical characteristics of the obtained polypropylene (a-8).

[Comparative Example 9]
In Comparative Example 8, the same procedure as in Comparative Example 8 was carried out except that the charged hydrogen was changed from 1.0 liter to 5.0 liter. Table 1 shows the results of evaluating the physical characteristics of the obtained polypropylene (a-9).

[Comparative Example 10]
In Comparative Example 8, the same procedure as in Comparative Example 8 was carried out except that the charged hydrogen was changed from 1.0 liter to 7.0 liter. Table 1 shows the results of evaluating the physical characteristics of the obtained polypropylene (a-10).

表１中の「オレフィン重合用触媒」の「外部ドナー」に関する記号の意味は以下のとおりである。
ii-1：シクロペンチルジエチルアミノジメトキシシラン
cii-1：ジシクロペンチルジメトキシシラン
cii-2：シクロヘキシルメチルジメトキシシラン
cii-3：ジイソプロピルジメトキシシラン
cii-4：２−イソブチル−２−イソプロピル−１，３−ジメトキシプロパン
cii-5：ジピロリジルジメトキシシラン
cii-6：ジエチルアミノトリエトキシシラン

The meanings of the symbols relating to "external donor" of "catalyst for olefin polymerization" in Table 1 are as follows.
ii-1: Cyclopentyl diethylaminodimethoxysilane
cii-1: dicyclopentyl dimethoxysilane
cii-2: Cyclohexylmethyldimethoxysilane
cii-3: diisopropyldimethoxysilane
cii-4: 2-isobutyl-2-isopropyl-1,3-dimethoxypropane
cii-5: dipyrrolidyldimethoxysilane
cii-6: diethylaminotriethoxysilane

[Examples 8 to 10 and Comparative Examples 11 to 13]
After mixing the polypropylene obtained in the above-mentioned Example or Comparative Example with the nucleating agent (F) or the inorganic fiber (G) so as to have the composition shown in Table 2 (however, Example 8 and Comparative Example 11). Then, only polypropylene was used.) A pellet-shaped propylene-based resin composition was prepared by melt-kneading with a twin-screw extruder under the following conditions. Using the obtained pellets, a test piece was prepared by injection molding with an injection molding machine under the following conditions. Table 2 shows the physical characteristics of the obtained injection molded product (test piece).

<Melting and kneading conditions>
Biaxial kneader in the same direction: Part number KZW-15, manufactured by Technobel Co., Ltd. Kneading temperature: 190 ° C
Screw rotation speed: 500 rpm
Feeder speed: 40 rpm
<Injection molding conditions>
Injection molding machine: EC40 (trade name, manufactured by Toshiba Machine Co., Ltd.)
Cylinder temperature: 190 ° C
Mold temperature: 40 ° C
Injection time-holding time: 13 seconds Cooling time: 15 seconds

[Examples 11-12 and Comparative Examples 14-16]
First, polypropylene and the propylene / α-olefin copolymer (B) are mixed in the amounts shown in Table 2, and then melt-kneaded with a twin-screw extruder under the following conditions to obtain a propylene-based block copolymer. Was prepared. Next, the ethylene / α-olefin copolymer (D) and the inorganic filler (E) were added to the obtained propylene-based block copolymer in the amounts shown in Table 2, and the conditions were as follows using a twin-screw extruder. To prepare a pellet-shaped propylene-based resin composition by melt-kneading with. Using the obtained pellets, a test piece was prepared by injection molding with an injection molding machine under the following conditions. Table 2 shows the physical characteristics of the obtained injection molded product (test piece).

<Melting and kneading conditions>
Biaxial kneader in the same direction: Part number KZW-15, manufactured by Technobel Co., Ltd. Kneading temperature: 190 ° C
Screw rotation speed: 500 rpm
Feeder speed: 40 rpm
<Injection molding conditions>
Injection molding machine: EC40 (trade name, manufactured by Toshiba Machine Co., Ltd.)
Cylinder temperature: 190 ° C
Mold temperature: 40 ° C
Injection time-holding time: 13 seconds Cooling time: 15 seconds

表２中の成分（Ｂ）および（Ｄ）〜（Ｇ）に関する記号の意味は以下のとおりである。
Ｂ−１：プロピレン・エチレン共重合体（商品名：タフマーＳ４０２０、三井化学（株）製）
Ｄ−１：エチレン・ブテン共重合体（商品名：タフマーＡ１０５０Ｓ、三井化学（株）製）
Ｅ−１：タルク（商品名：ＪＭ２０９、浅田製粉（株）製）
Ｆ−１：フォスフェート系核剤（商品名：アデカスタブＮＡ−１１、（株）ＡＤＥＫＡ製）
Ｇ−１：塩基性硫酸マグネシウム無機繊維（商品名：モスハイジＡ、宇部マテリアルズ（株）製）

The meanings of the symbols relating to the components (B) and (D) to (G) in Table 2 are as follows.
B-1: Propylene / ethylene copolymer (trade name: Toughmer S4020, manufactured by Mitsui Chemicals, Inc.)
D-1: Ethylene-butene copolymer (trade name: Toughmer A1050S, manufactured by Mitsui Chemicals, Inc.)
E-1: Talc (trade name: JM209, manufactured by Asada Flour Milling Co., Ltd.)
F-1: Phosphate-based nucleating agent (trade name: ADEKA STAB NA-11, manufactured by ADEKA CORPORATION)
G-1: Basic magnesium sulfate inorganic fiber (trade name: Mosheidi A, manufactured by Ube Material Industries Ltd.)

Claims (9)

Propylene-based polymer characterized by satisfying the following requirements (1) to (4):
(1) The meso average chain length is 1665 to 100,000;
(2) Melt flow rate (MFR) (ASTM D1238, 230 ° C., under a 2.16kg load) is 17 to 1000 g / 10 min;
(3) The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is 4.2 to 20;
(4) When the ratio of the components eluted at a temperature of 122 ° C. or higher is A% by weight and the melt flow rate of the above requirement (2) is Bg / 10 minutes by the temperature rise elution fractionation measurement method (TREF), the following formula is used. (I) is satisfied.
100 ≧ A ≧ 20 × EXP (−0.01 × B) ・ ・ ・ (I) Propylene-based polymer characterized by satisfying the following requirements (1) to (5):
(1) The meso average chain length is 1665 to 100,000;
(2) Melt flow rate (MFR) (ASTM D1238, 230 ° C., under a 2.16kg load) is 17 to 1000 g / 10 min;
(3) The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is 4.2 to 20;
(4) When the ratio of the components eluted at a temperature of 122 ° C. or higher is A% by weight and the melt flow rate of the above requirement (2) is Bg / 10 minutes by the temperature rise elution fractionation measurement method (TREF), the following formula is used. Satisfy (I);
100 ≧ A ≧ 20 × EXP (−0.01 × B) ・ ・ ・ (I)
(5) The amount of the n-decane-soluble component at 23 ° C. is 0.01 to 2% by weight. The method for producing a propylene-based polymer according to claim 1 or 2, wherein propylene is polymerized in the presence of a catalyst for olefin polymerization.
The catalyst for olefin polymerization
(I) A solid titanium catalyst component containing magnesium, titanium, halogen and an electron donor and satisfying the following requirements (k1) to (k4).
(Ii) The organosilicon compound component represented by the following formula (II) and
(Iii) A catalyst [A] containing an organometallic compound component containing an element belonging to Group 1, Group 2, or Group 13 of the Periodic Table, or
A catalyst [B] containing a prepolymerization catalyst (p) in which propylene is prepolymerized on the catalyst [A], the organosilicon compound component (ii), and the organometallic compound component (iii).
A method for producing a propylene-based polymer, which is characterized by being:
(K1) Titanium content is 2.5% by weight or less;
(K2) The content of the electron donor is 8 to 30% by weight;
(K3) Electron donor / titanium (weight ratio) is 7 or more;
(K4) Titanium is not substantially desorbed by hexane washing at room temperature.
R ¹ Si (OR ² ) ₂ (NR ³ R ⁴ ) ・ ・ ・ (II)
[In formula (II), R ¹ represents a secondary or tertiary hydrocarbon group having 1 to 20 carbon atoms, R ² represents a hydrocarbon group having 1 to 4 carbon atoms, and R ³ represents a hydrocarbon group having 1 to 4 carbon atoms. It represents 12 hydrocarbon groups or hydrogen atoms, and R ⁴ represents a hydrocarbon group having 1 to 12 carbon atoms. ] The solid titanium catalyst component (i)
(A) Solid titanium, which contains magnesium, titanium, halogen and electron donors, and titanium is not desorbed by hexane washing at room temperature.
(B) Aromatic hydrocarbons,
The method for producing a propylene-based polymer according to claim 3, wherein (c) is produced by a method including a step of contacting liquid titanium and (d) an electron donor. 20 to 80% by mass of a propylene-based block copolymer (C) composed of a propylene homopolymer portion and a propylene / α-olefin copolymer portion,
Ethylene-α-olefin copolymers (D) 1 to 50 containing 50 to 95 mol% of a structural unit derived from ethylene and 5 to 50 mol% of a structural unit derived from an α-olefin having 3 to 20 carbon atoms. Mass% and Inorganic Filler (E) 0-70 Mass%
(However, the total of the components (C), (D) and (E) is 100% by mass).
The propylene-based block copolymer (C) is
As the propylene homopolymer part, 60 to 99% by mass of the propylene-based polymer (A) according to claim 1 or 2, and as the propylene / α-olefin copolymer part, a structural unit derived from propylene 55 to It contains 1 to 40% by mass of a propylene / α-olefin copolymer (B) containing 90 mol% and 10 to 45 mol% of a structural unit derived from an α-olefin having 2 to 20 carbon atoms other than propylene (). However, the total of the components (A) and (B) is 100% by mass.),
Propylene resin composition. A propylene-based resin composition containing 100 parts by mass of the propylene-based polymer (A) according to claim 1 or 2 and 0.01 to 10 parts by mass of a nucleating agent (F). Selected from the group consisting of the propylene-based polymer (A) according to claim 1 or 2 and the propylene-based block copolymer (C) composed of a propylene homopolymer portion and a propylene / α-olefin copolymer portion. At least one component 70-99.5% by mass,
Inorganic fiber (G) containing 0.5 to 30% by mass (provided that the total of components (A), (C) and (G) is 100% by mass).
The propylene-based block copolymer (C) is
As the propylene homopolymer part, 60 to 99% by mass of the propylene-based polymer (A) according to claim 1 or 2, and as the propylene / α-olefin copolymer part, a structural unit derived from propylene 55 to It contains 1 to 40% by mass of a propylene / α-olefin copolymer (B) containing 90 mol% and 10 to 45 mol% of a structural unit derived from an α-olefin having 2 to 20 carbon atoms other than propylene (). However, the total of the components (A) and (B) is 100% by mass.),
Propylene resin composition. A molded product containing the propylene-based polymer according to claim 1 or 2. A molded product formed by using the propylene-based resin composition according to any one of claims 5 to 7.